O. F. Mironova

Physicochemical parameters of the formation of hydrothermal deposits: A fluid inclusion study. I. Tin and tungsten deposits

The author’s database, which presently includes data from more than 18500 publications on fluid and melt inclusions in minerals and is continuing to be appended, was used to generalize results on physicochemical parameters of the formation of hydrothermal deposits and occurrences of tin and tungsten. The database includes data on 320 tin and tin-tungsten deposits and occurrences and 253 tungsten and tungstentin deposits around the world. For most typical minerals of these deposits (quartz, cassiterite, tungsten, scheelite, topaz, beryl, tourmaline, fluorite, and calcite), histograms of homogenization temperatures of fluid inclusions were plotted. Most of 463 determinations made for cassiterite are in the range of 300–500°C with maximum at 300–400°C, while those for wolframite and scheelite (453 determinations) fall in the range of 200–400°C with maximum at 200–300°C. Representative material on pressures of hydrothermal fluids included 330 determinations for tin and 430 determinations for tungsten objects. It was found that premineral, ore, and postmineral stages spanned a wide pressure range from 70–110 bar to 6000–6400 bar. High pressures of the premineral stages at these deposits are caused by their genetic relation with felsic magmatism. Around 50% of pressure determinations lie in the range of 500–1500 bar. The wide variations in total salinity and temperatures (from 0.1 to 80 wt % NaCl equiv and 20–800°C) were obtained for mineral-forming fluids at the tin (1800 determinations) and tungsten (2070 determinations) objects. Most of all determinations define a salinity less than 10 wt % NaCl equiv. (∼60%) and temperature range of 200–400°C (∼70%). The average composition of volatile components of fluids determined by different methods is reported. Data on gas composition of the fluids determined by Raman spectroscopy are examined. Based on 180 determinations, the fluids from tin objects have the following composition (in mol %): 41.2 CO2, 39.5 CH4, 19.15 N2, and 0.15 H2S. The volatile components of tungsten deposits (190 determinations) are represented by 56.1 CO2, 30.7 CH4, 13.2 N2, and 0.01 H2S. Thus, the inclusions of tungsten deposits are characterized by higher CO2 content and lower (but sufficiently high) contents of CH4 and N2. The concentrations of tin and tungsten in magmatic melts and mineral-forming fluids were estimated from analysis of individual inclusions. The geometric mean Sn contents are 87 ppm (+ 610 ppm/−76 ppm) in the melts (569 determinations) and 132 ppm (+ 630 ppm/−109 ppm) in the fluids (253 determinations). The geometric mean W values are 6.8 ppm (+ 81/−6.2 ppm) in the magmatic melts (430 determinations) and 30 ppm (+ 144 ppm/−25 ppm) in the mineral-forming fluids (391 determinations).

Principal Physicochemical Parameters of Natural Mineral-Forming Fluids

The authors’ database (which includes data from more than 17500 publications on fluid and melt inclusions in minerals) was used to generalize information on the principal physicochemical parameters of natural mineral-forming fluids (temperature, pressure, density, salinity of aqueous solutions, and the gas composition of the fluids). For 21 minerals, data are reported on the frequency of occurrence of the homogenization temperatures of fluid inclusions in various temperature ranges, which make it possible to reveal temperature ranges most favorable for the crystallization of these minerals. Data on 5260 determinations were used to evaluate the frequency of occurrence of certain temperature and pressure ranges of natural fluids within the temperature intervals of 20–1200°C and 1–12000 bar. Within these intervals, frequencies of occurrence were evaluated for water-dominated and water-poor or water-free fluid inclusions in minerals. The former are predominant at temperatures below 600°C and pressures below 4000 bar, whereas the latter dominate at temperatures of 600–1200°C and pressures of 4000-12000 bar. Illustrative examples are presented for visually discernible magmatic water that exists as an individual high-density phase in melt inclusions in minerals from various rocks sampled worldwide (in the Caucasus, Italy, Slovakia, United States, Uzbekistan, New Zealand, Chile, and others). Attention is drawn to the fact that extensive data testify to fairly high (>1000–1500 bar) pressures during hydrothermal mineral-forming processes. These pressures are much higher not only than the hydrostatic but also the lithostatic pressures of the overlying rocks. Data on more than 18000 determinations are used to evaluate the frequency of occurrence of certain temperature and salinity ranges of mineral-forming fluids within the intervals of 20–1000°C and 0–80 wt % equiv. NaCl and certain temperature and density ranges of these fluids at 20–1000°C and 0.01–1.90 g/cm3. Information is presented on the gas analysis methods most commonly applied to natural fluids in studying fluid inclusions in minerals in 1965–2007. The average composition of the gaseous phase of natural inclusions is calculated based on more than 3000 Raman spectroscopic analyses (the most frequently used method for analyzing individual inclusions).

Volatile components of natural fluids: Evidence from inclusions in minerals: Methods and results

A database compiled by the author on volatile components in fluid inclusions (5300 analyses compiled from 300 publications) was used to compare destructive and nondestructive analytical techniques and thermal and mechanical methods for the extraction of volatiles in destructive techniques. Possible explanations are proposed for opposite conclusions published by various researchers. The paper summarizes the principal outcomes of the long-lasting discussion on the optimal methods able to provide the most reliable results. No unambiguous answer is provided. Analysis of extensive literature data indicates that each of the techniques is characterized by its own advantages and disadvantages, and an optimal solution should be selected with regard for the materials to be analyzed and formulated tasks. In any event, the results require careful interpretation. The average composition of natural fluids calculated from extensive statistical material is as follows (mol %): 70.3 H2O, 21.4 CO2, 6.3 CH4, 2.0 N2, and 0.07 H2S. The distribution of volatile components was examined in minerals from hydrothermal ore deposits of various types (gold, tungsten, tin, and base-metal) and metamorphic rocks

Physicochemical formation parameters of hydrothermal mineral deposits: Evidence from fluid inclusions. II. Gold, silver, lead, and zink deposits

Information from a database, which was compiled and continuously updated by the authors of this paper and now includes information from 19500 publication on fluid and melt inclusions in minerals, is used to summarize results on the physicochemical formation parameters of hydrothermal Au, Ag, Pb, and Zn deposits. The database provides information on fluid inclusions in minerals from 970 Pb-Zn, 220 Au-Ag-Pb-Zn, and 825 Au-Ag deposits in various settings worldwide. Histograms for the homogenization temperatures of fluid inclusion are presented for the most typical minerals of the deposits. In sphalerite, most homogenization temperatures (1327 measurements) of fluid inclusions lie within the range of 50–200°C with a maximum at 100–200°C for this mineral from Pb-Zn deposits and within the range of 100–350°C (802 measurements) with a maximum at 200–300°C for this mineral from Au deposits. Data are presented on fluid pressures at Au (1495 measurements) and Pb-Zn (180 measurements) deposits. The pressure during the preore, ore-forming, and postore stages at these deposits ranged from 4–10 to 6000 bar. The reason for the high pressures during preore stages at the deposits is the relations of the fluids to acid magmatic and metamorphic processes. More than 70% of the fluid pressures values measured at Pb-Zn deposits lie within the range of 1–1500 bar. Au-Ag deposits are characterized by higher fluid pressures of 500–2000 bar (61% of the measurements). The overall ranges of the salinity and temperature of the mineral-forming fluid at Au-Ag (6778 measurements) and Pb-Zn (3395 measurements) deposits are 0.1–80 wt % equiv. NaCl and 20–800°C. Most measurements (∼64%) for Au-Ag deposits yield fluid salinity <10 wt % equiv. NaCl and temperatures of 200–400°C (63%). Fluids at Pb-Zn deposits are typically more saline (10–25 wt % equiv. NaCl, 51% measurements) and lower temperature (100–300°C, 74% measurements). Several measurements of the fluid density fall within the range of 0.8–1.2 g/cm3. The average composition of volatile components of the fluids was evaluated by various techniques. The average composition of volatile components of fluid inclusions in minerals is calculated for hydrothermal W, Au, Ag, Sn, and Pb-Zn deposits, metamorphic rocks, and all geological objects. The Au, Ag, Pb, and Zn concentrations in magmatic melts and mineral-forming fluids is evaluated based on analyses of individual inclusions.

Sources of high-pressure fluids involved in the formation of hydrothermal deposits

Available fluid inclusion data on hydrothermal deposits, deep-seated xenoliths, magmatic and metamorphic rocks were used to generalize the determinations of physicochemical parameters (temperature, pressure, and compositions) of natural fluids. It was established that fluid pressures during formation of hydrothermal deposits often exceeded lithostatic loading (250–270 bar/km) of the overlying rocks. Fluids from deep-seated xenoliths, magmatic and metamorphic objects are considered as the possible sources of high-pressure fluids. Data on temperatures, pressures, and fluid composition are generalized for each object.

Physicochemical parameters of formation of hydrothermal deposits: Evidence from fluid inclusions. III. Uranium deposits

An original database, which was compiled by the authors, is continuously updated, and now contains data from more than 19 800 publications on fluid and melt inclusions in minerals, was utilized to review and synthesize data on the physicochemical parameters at which hydrothermal uranium deposits and occurrences were formed. The parameters discussed below are temperature, pressure, density, salinity, gas composition of the fluid, and U concentration in the hydrothermal fluid. The database contains data of fluid inclusions in minerals from 90 U deposits and occurrences worldwide. Histograms of the homogenization temperatures of fluid inclusions are presented for such typical minerals of these deposits and occurrences as quartz, calcite, and fluorite. The temperature range most favorable for the origin of U deposits is 100–200°C (67% of the 937 measured temperature values fall within this range), which makes U deposits remarkably different from higher temperature Au-Ag, W, and Sn deposits. These deposits also differ in the salinity of the fluids. The range of fluid salinity of 10–30 wt % equiv. NaCl includes 42% of fluid salinity values measured at U deposits (our database includes 937 measured values), 27% for Au-Ag deposits (10 237 measured values), 27% for W deposits (2333 measured values), and for Sn deposits (1981 measured values). The relatively low temperature of U-bearing fluids and their high salinity testify that these solutions had a high density: 94% of all measured values lie within the range of 0.8–1.2 g/cm3. Fluid pressure at U deposits broadly varied from 2500 to 300 bar and perhaps even lower values. Data on the chemical composition of the gas phase of the fluid inclusions show a significant diversity of the fluids contained in the inclusions. In certain instances, H2O-CO2 fluids give way to fluids rich in CH4 and N2 with minor amounts of hydrocarbons. Data are reported on the gas composition of fluid inclusions in the nuclear-reactor zone at three Precambrian U deposits. Analyses of individual inclusions were utilized to evaluate U concentrations in magmatic melts and mineral-forming fluids. The geometric mean U concentration in silicate melts of composition ranging from ultramafic to silicic is 0.92 ppm (8053 measured values), and the analogous values for the fluids is 1.21 ppm (271 measured values).

Physicochemical parameters of the origin of hydrothermal mineral deposits: Evidence from fluid inclusions. IV. Copper and molybdenum deposits

Physicochemical parameters of the origin of Cu and Mo deposits are reviewed based on an original database that currently includes information from more than 21000 publications on fluid and melt inclusions hosted in various minerals. The deposits are classified into three types: (i) Cu–Mo (usually porphyry), (ii) Cu (usually without Mo but often with base metals), and (iii) Mo (without Cu but often with Be and W). For these deposits, the temperature and pressure of their origin and the density, salinity, and gas composition of the fluids are discussed. The average composition of the dominant volatile components of natural fluids is reported for Cu and Mo deposits and is compared with the composition of volatiles in fluids at Au, Sn, W, Pb, and Zn deposits. Data on individual inclusions are used to evaluate the Cu and Mo concentrations in the magmatic silicate melts and mineral-forming fluids.

Composition of Volatile Components in Mineral-Hosted Fluid Inclusions at Hydrothermal Deposits. Water–Rock–Gas Systems in Ore-Forming Processes

The paper presents data on the average analyzed concentrations of volatile components (CO2, CH4 and other hydrocarbons, N2, and H2S) in natural fluids producing hydrothermal Au, Sn, W, Mo, Cu, Pb, and Zn mineral deposits. Characteristics of the gas regime at these deposits are determined. Thermodynamic simulations are carried out to model how compounds with volatile components are formed when water interacts with silicic and mafic rocks within wide P–T ranges. The speciation of volatile components determined by direct analysis is in good agreement with numerical simulations of water–rock systems (for silicic and mafic rocks). More reduced species with volatile components are formed in mafic rocks.

Physicochemical parameters and geochemical features of fluids of precamrbian gold deposits

This paper analyzes literature data on physicochemical parameters and chemical composition of fluids of Precambrian endogenous gold deposits. The average values and ranges of temperature, pressure, and salinity of fluids from the Archean and Proterozoic gold deposits are estimated. It is revealed that fluids of Archean deposits are dominated by methane, while those of Proterozoic deposits, by nitrogen. It is proposed that the accumulation of nitrogen in the atmosphere is related to the intense nitrogen degassing from the Earth’s interior. The highest pressures of endogenous fluids in this period could reflect specifics of deep geodynamics of the planet in the Proterozoic. The large gold deposits (>100 tons) are characterized by narrower range of physicochemical parameters as compared to small deposits. The contribution of heated chloride brines in the formation of majority of large Proterozoic deposits is established.